Manufacturing method of solid catalyst for propylene polymerization

ABSTRACT

Disclosed is a method for preparing a solid catalyst for propylene polymerization, specifically to a method for preparing a solid catalyst for propylene polymerization which can produce a polypropylene having high melt flow rate, a wide molecular distribution and excellent stereoregularity with a high production yield.

TECHNICAL FIELD

The present invention is directed to a method for preparing a solidcatalyst for propylene polymerization, specifically to a method forpreparing a solid catalyst for propylene polymerization which canproduce a polypropylene having high melt flow rate, a wide moleculardistribution and excellent stereoregularity with a high productionyield.

BACKGROUND OF THE INVENTION

Polypropylene is very useful in industrial point of view and has variousindustrial applications, particularly it is widely applied to materialsused in automobiles and electronic products, etc. for various usages.However, in order to even further broaden the applications ofpolypropylene, it is still needed to make an improvement in rigidity andprocessability which can be led by increasing a stereoregularity andwidening a molecular weight distribution.

For polymerization of olefins such as propylene or the like, a solidcatalyst comprising magnesium, titanium, an electron donor and halogenas essential elements is known in this field of art, and methods forpolymerizing or copolymerizing olefins which use a catalyst systemcomprised of said solid catalyst, an organoaluminum compound and anorganosilicon compound have been proposed many. However, such methodsare not satisfying in terms of obtaining polymers having highstereoregularity with a high production yield, and thus needed to beimproved in the above aspect.

As a method so as to reduce the production cost by increasing thecatalyst polymerization activity and improve physical properties of theresulted polymers by improving the catalyst performance such asstereoregularity, it is generally known in this field of art to usediester of aromatic dicarboxylic acid as an internal electron donor andrelated patent applications have been filed many. For examples, U.S.Pat. No. 4,562,173, U.S. Pat. No. 4,981,930, Korean Patent No. 0072844and the like. The above patents describe a method for preparing acatalyst showing high activity and stereoregularity by using aromaticdialkyldiesters or aromatic monoalkylmonoesters. However, the methods ofsaid patents cannot provide high stereoregular polymers with a highyield to the satisfying degree and thus still needed to be improved.

There have been many approaches to increase the molecular weightdistribution of a polymer. For example, U.S. Pat. No. 6,376,628 B1proposes a method for broadening the molecular weight distribution bypolymerizing propylene by using a solid catalyst component composed ofmagnesium, titanium, halogen and an electron donor, in the presence ofan organoaluminum compound and an isoquinoline silicon compound, andthis method is needed to be improved in terms of catalyst activity andflowability.

WO 00/63261 proposes a method for producing polymers having highstereoregularity and wide molecular weight distribution by usingsuccinates as an internal electron donor, however, it fails to disclosean example of using dialkylalkylidene succinate. Further, said methodstill needs to be improved in molecular weight distribution.

DETAILED DESCRIPTION OF THE INVENTION

The present invention has been developed to solve the problems of priorarts as described above, and thus the purpose of the present inventionis to provide a method for preparing a solid catalyst for propylenepolymerization which can produce polypropylene simultaneously havinghigh melt flow rate, wide molecular weight distribution and excellentstereoregularity with high production yield.

In order to achieve the purpose of the present invention, the presentinvention provides a method for preparing a solid catalyst characterizedby comprising the following steps:

(1) reacting dialkoxymagnesium and a titanium halide, in the presence ofan organic solvent;(2) adding an internal electron donor selected from the compoundsrepresented by the following formula (II) together with another internalelectron donor selected from the compounds represented by the followingformula (III) or (IV) to the resulted product from the above step (1),and mixing them together, while elevating the temperature to the rangeof 80-130° C.,

(wherein, R¹, R², R³ and R⁴ are independently a linear, branched orcyclic C1-10 alkyl group or hydrogen);

(wherein, R¹ and R² are independently a linear, branched or cyclic C1-10alkyl group or hydrogen; and R³ and R⁴ are independently a linear,branched or cyclic C1-10 alkyl group)

(wherein, R¹, R² and R⁴ are independently a linear, branched or cyclicC1-10 alkyl group or hydrogen; R³ is a linear, branched or cyclic C1-10alkyl group); and(3) reacting titanium halide with the resulted product from the abovestep (2) at the temperature range of 80-130° C. and washing the resultedproduct.

Although the organic solvent used in the above step (1) is notspecifically limited, preferably used may be C6-12 aliphatic, aromaticor halogenated hydrocarbons, more preferably C7-10 saturated aliphatic,aromatic or halogenated hydrocarbons, and for example, at least oneselected from the group consisting of octane, nonane, decane, tolueneand xylene, chlorobutane, chlorohexane, chloroheptane or the like may beused alone or as a mixture.

The dialkoxymagnesium used in the above step (1) is obtained by reactingmetal magnesium with an alcohol anhydride in the presence of magnesiumchloride and thus formed as spherical particles having an averageparticle diameter of 10-200 μm with a smooth surface. Such sphericalparticle shape is preferred to be remained as it is during the propylenepolymerization process. When the average particle size is less than 10μm, the amount of microparticles are increased in the resulted catalystsand when it is more than 200 μm, bulk density is likely to get smaller,disadvantageously.

Further, the ratio of the organic solvent to dialkoxymagnesium, i.e.dialkoxymagnesium(by weight): organic solvent(by volume) is preferably1:5-50, more preferably 1:7-20. When the ratio of is less than 1:5,viscosity of the slurry becomes rapidly increased, thereby hinderinghomogeneous stirring, and when it is more than 1:50, the bulk density ofthe resulted carrier becomes significantly reduced or the particlesurface becomes rough, disadvantageously.

The titanium halides used in the above step (1) of the method forpreparing a solid catalyst according to the present invention may bepreferably represented as the following formula (I):

Ti(OR)_(a)X_((4-a))  (I)

wherein, R is a C1-10 alkyl group; X is a halogen atom; a is an integerof 0-3 for the atomic valence in the above formula (I). Particularly,titanium tetrachloride is preferably used. The step (1) of the methodfor preparing a solid catalyst is preferably carried out by graduallyadding titanium halide to the dialkoxymagnesium suspended in the organicsolvent at a temperature range of 0° C.-30° C.

The amount of titanium halide used in the above step (1) is preferably0.1-10 moles, more preferably 0.3-2 moles, based on 1 mole ofdialkoxymagnesium. When the amount is less than 0.1 mole, the conversionof dialkoxymagnesium to magnesium chloride does not smoothly proceed,and when the amount is more than 10 moles, an excessive amount oftitanium components are present in the resulted catalyst,disadvantageously.

As for the internal electron donor used in the above step (2) of themethod for preparing a solid catalyst, a mixture of an internal electrondonor selected from the compounds represented by the following formula(II) and another internal electron donor selected from the compoundsrepresented by the following formula (III) or (IV) may be used.

(wherein, R¹, R², R³ and R⁴ are independently a linear, branched orcyclic C1-10 alkyl group or hydrogen)

(wherein, R¹ and R² are independently a linear, branched or cyclic C1-10alkyl group or hydrogen; and R³ and R⁴ are independently a linear,branched or cyclic C1-10 alkyl group)

(wherein, R¹, R² and R⁴ are independently a linear, branched or cyclicC1-10 alkyl group or hydrogen; R³ is a linear, branched or cyclic C1-10alkyl group).

As for the examples of the internal electron donor, the followings maybe mentioned: diethyl-2,3-dimethylsuccinate,diethyl-2,3-diethylsuccinate, diethyl-2,3-dipropylsuccinate,diethyl-2,3-diisopropylsuccinate, diethyl-2,3-dibutylsuccinate,diethyl-2,3-diisobutylsuccinate, diethyl-2,3-dipentylsuccinate,diethyl-2,3-dihexylsuccinate, diethyl-2,3-dicyclopentylsuccinate,diethyl-2,3-dicyclohexylsuccinate,diethyl-2-cyclopentyl-3-methylsuccinate,diethyl-2-cyclohexyl-3-methylsuccinate,diethyl-2-isopropyl-3-methylsuccinate,diethyl-2-isobutyl-3-methylsuccinate,diethyl-2-cyclopentyl-3-ethylsuccinate,diethyl-2-cyclohexyl-3-ethylsuccinate,diethyl-2-isopropyl-3-ethylsuccinate,diethyl-2-isobutyl-3-ethylsuccinate,diethyl-2-cyclopentyl-3-propylsuccinate,diethyl-2-cyclohexyl-3-propylsuccinate,diethyl-2-isopropyl-3-propylsuccinate,diethyl-2-isobutyl-3-propylsuccinate,diethyl-2-cyclopentyl-3-isopropylsuccinate,diethyl-2-cyclohexyl-3-isopropylsuccinate,diethyl-2-isobutyl-3-isopropylsuccinate,diethyl-2-cyclopentyl-3-isobutylsuccinate,diethyl-2-cyclohexyl-3-isobutylsuccinate,diethyl-2-isopropyl-3-isobutylidenesuccinate,diethyl-2,3-dimethylidenesuccinate, diethyl-2,3-diethylidenesuccinate,diethyl-2,3-dipropylidenesuccinate,diethyl-2,3-diisopropylidenesuccinate,diethyl-2,3-dibutylidenesuccinate, diethyl-2,3-diisobutylidenesuccinate,diethyl-2,3-dipentylidenesuccinate, diethyl-2,3-dihexylidenesuccinate,diethyl-2,3-dicyclopentylidenesuccinate,diethyl-2,3-dicyclohexylidenesuccinate,diethyl-2-cyclopentyl-3-methylidenesuccinate,diethyl-2-cyclohexyl-3-methylidenesuccinate,diethyl-2-isopropyl-3-methylidenesuccinate,diethyl-2-isobutyl-3-methylidenesuccinate,diethyl-2-cyclopentyl-3-ethylidenesuccinate,diethyl-2-cyclohexyl-3-ethylidenesuccinate,diethyl-2-isopropyl-3-ethylidenesuccinate,diethyl-2-isobutyl-3-ethylidenesuccinate,diethyl-2-cyclopentyl-3-propylidenesuccinate,diethyl-2-cyclohexyl-3-propylidenesuccinate,diethyl-2-isopropyl-3-propylidenesuccinate,diethyl-2-isobutyl-3-propylidenesuccinate,diethyl-2-cyclopentyl-3-isopropylidenesuccinate,diethyl-2-cyclohexyl-3-isopropylidenesuccinate,diethyl-2-isobutyl-3-isopropylidenesuccinate,diethyl-2-cyclopentyl-3-isobutylidenesuccinate,diethyl-2-cyclohexyl-3-isobutylidenesuccinate,diethyl-2-isopropyl-3-isobutylidenesuccinate,diethyl-2-cyclopentylidene-3-methylsuccinate,diethyl-2-cyclohexylidene-3-methylsuccinate,diethyl-2-isopropylidene-3-methylsuccinate,diethyl-2-isobutylidene-3-methylsuccinate,diethyl-2-cyclopentylidene-3-ethylsuccinate,diethyl-2-cyclohexylidene-3-ethylsuccinate,diethyl-2-isopropylidene-3-ethylsuccinate,diethyl-2-isobutylidene-3-ethylsuccinate,diethyl-2-cyclopentylidene-3-propylsuccinate,diethyl-2-cyclohexylidene-3-propylsuccinate,diethyl-2-isopropylidene-3-propylsuccinate,diethyl-2-isobutylidene-3-propylsuccinate,diethyl-2-cyclopentylidene-3-isopropylsuccinate,diethyl-2-cyclohexylidene-3-isopropylsuccinate,diethyl-2-isobutylidene-3-isopropylsuccinate,diethyl-2-cyclopentylidene-3-isobutylsuccinate,diethyl-2-cyclohexylidene-3-isobutylsuccinate,diethyl-2-isopropylidene-3-isobutylsuccinate and the like.

The above step (2) is preferably carried out by while graduallyincreasing the temperature of the product resulted from the step (1) tothe range of 80-130° C., adding an internal electron donor mixturethereto and allowing for them to react for 1-3 hours. When thetemperature is less than 80° C. or the reaction time is less than 1hour, the reaction can be hardly completed, and when the temperature ismore than 130° C. or the reaction time is more than 3 hours, aside-reaction may occur and lower the polymerization activity of theresulted catalyst or stereoregularity of the resulted polymers.

The temperature or the number of adding an internal electron donor, aslong as it is added during the temperature elevation process, is notspecifically limited, and the total amount of the internal electrondonor used is preferably 0.1-1.0 mole based on 1 mole ofdialkoxymagnesium. When the amount is out of said range, thepolymerization activity of the resulted catalyst or stereoregularity ofthe resulted polymers may be decreased disadvantageously.

The step (3) of the solid catalyst preparation process according to thepresent invention is a process in which the product resulted from theabove step (2) secondarily reacts with titanium halide at thetemperature range of 80-130° C. As for exemplary titanium halide used inthis step, titanium halide having the above general formula (I) may bementioned. The reactions at each step of the above solid catalystpreparation method are preferably carried out in a reactor equipped witha stirrer from which moisture was sufficiently removed, under nitrogenatmosphere.

The solid catalyst prepared by the above method of the present inventionis formed by comprising magnesium, titanium, halogen and an internalelectron donor, and preferably comprising magnesium 5-40 wt %, titanium0.5-10 wt %, halogen 50-85 wt % and an internal electron donor mixture2.5-30 wt % in terms of the catalyst activity.

The solid catalyst of the present invention may be suitably used inpropylene polymerization or copolymerization, and the method forpolypropylene (co)polymerization using the solid catalyst obtained bythe present invention comprises polymerization of propylene orco-polymerization of propylene with other alpha-olefins in the presenceof the solid catalyst, a cocatalyst and an external electron donor.

The solid catalyst may be prepolymerized with ethylene or alpha-olefinsbefore being used as a component of a polymerization reaction.

The prepolymerization reaction may be carried out at a sufficiently lowtemperature under the pressure of ethylene or alpha-olefin, in thepresence of hydrocarbon solvent such as hexane, said catalyst componentand organoaluminum compound such as triethylaluminum. Theprepolymerization by which catalyst particles are surrounded by polymersso as to maintain the catalyst shape, helps improve the polymermorphology after polymerization. The weight ratio of polymers/catalystafter completion of prepolymerization is preferably about 0.1-20:1.

As a cocatalyst component for the polypropylene (co)polymerizationmethod of the present invention, organometallic compounds belonging toGroup II or III of the Periodic table of element may be used, forexample alkylaluminum compounds are preferably used. The alkylaluminumcompounds are represented by the following formula (V):

AlR₃  (V)

wherein, R is a C1-8 alkyl group.

As for the specific examples of such alkylaluminum compounds,trimethylaluminum, triethylaluminum, tripropylaluminum,tributylaluminum, triisobutylaluminum and trioctylaluminum or the likemay be mentioned.

The ratio of the cocatalyst to the solid catalyst component may bevaried depending on a polymerization method used, however the molarratio of the metal element of the cocatalyst to the titanium element inthe solid catalyst component is preferably the range of 1-1000 and morepreferably the range of 10-300. When the molar ratio of the metalelement, for example such as aluminum in the cocatalyst to the titaniumelement in the solid catalyst component is out of said range of 1-1000,the polymerization activity is significantly degraded,disadvantageously.

As for the external electron donor used in the method for preparingpolypropylene according to the present invention, at least one speciesof alkoxy silane compounds represented by the following formula (VI) maybe used:

R¹ _(m)R² _(n)Si(OR³)_((4-m-n))  (VI)

wherein, R¹ and R², which may be same or different are a linear,branched or cyclic C1-12 alkyl or aryl group; R³ is a linear or branchedC1-6 alkyl group; m and n is respectively, 0 or 1; and m+n is 1 or 2.

Specific examples of the external electron donor include the followingcompounds, and it may be used alone or as a mixture of one or more:n-propyltrimethoxysilane, di-n-propyldimethoxysilane,isopropyltrimethoxysilane, diisopropyldimethoxysilane,n-butyltrimethoxysilane, di-n-butyldimethoxysilane,isobutyltrimethoxysilane, diisobutyldimethoxysilane,tert-butyltrimethoxysilane, di-tert-butyldimethoxysilane,n-pentyltrimethoxysilane, di-n-pentyldimethoxysilane,cyclopentyltrimethoxysilane, dicyclopentyldimethoxysilane,cyclopentylmetyldimethoxysilane, cyclopentylethyldimethoxysilane,cyclopentylpropyldimethoxysilane, cyclohexyltrimethoxysilane,dicyclohexyldimethoxysilane, cyclohexylmetyldimethoxysilane,cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane,cycloheptyltrimethoxysilane, dicycloheptyldimethoxysilane,cycloheptylmetyldimethoxysilane, cycloheptylethyldimethoxysilane,cycloheptylpropyldimethoxysilane, phenyltrimethoxysilane,diphenyldimethoxysilane, phenylmetyldimethoxysilane,phenylethyldimethoxysilane, phenylpropyldimethoxysilane,n-propyltriethoxysilane, di-n-propyldiethoxysilane,isopropyltriethoxysilane, diisopropyldiethoxysilane,n-butyltriethoxysilane, di-n-butyldiethoxysilane,isobutyltriethoxysilane, diisobutyldiethoxysilane,tert-butyltriethoxysilane, di-tert-butyldiethoxysilane,n-pentyltriethoxysilane, di-n-pentyldiethoxysilane,cyclopentyltriethoxysilane, dicyclopentyldiethoxysilane,cyclopentylmetyldiethoxysilane, cyclopentylethyldiethoxysilane,cyclopentylpropyldiethoxysilane, cyclohexyltriethoxysilane,dicyclohexyldiethoxysilane, cyclohexylmetyldiethoxysilane,cyclohexylethyldiethoxysilane, cyclohexylpropyldiethoxysilane,cycloheptyltriethoxysilane, dicycloheptyldiethoxysilane,cycloheptylmetyldiethoxysilane, cycloheptylethyldiethoxysilane,cycloheptylpropyldiethoxysilane, phenyltriethoxysilane,diphenyldiethoxysilane, phenylmetyldiethoxysilane,phenylethyldiethoxysilane, phenylpropyldiethoxysilane and the like.

The amount of external electron donor may be slightly varied dependingon the polymerization method applied thereto, however the molar ratio ofthe silicon atom in the external electron donor based on the titaniumatom in the catalyst component is preferably in the range of 0.1-500 andmore preferably 1-100. When the molar ratio of the silicon atom in theexternal electron donor to the titanium atom in the catalyst componentis less than 0.1, stereoregularity of the resulted propylene polymerbecomes significantly lowered, disadvantageously, and when it is morethan 500, polymerization activity of the catalyst is significantlydecreased.

During the propylene polymerization or copolymerization reaction, thepolymerization temperature is preferably 20-120° C.

When the polymerization temperature is less than 20° C., thepolymerization reaction cannot sufficiently proceed, and when it is morethan 120° C., the activity is considerably lowered and the physicalproperties of the resulted polymers is degraded, disadvantageously.

EXAMPLES

Hereinafter, the present invention is further described through thefollowing examples, in detail. However, it should be understood that theexamples are only provided on illustrative purposes without anyintention to limit the scope of the present invention.

Example 1 1. Preparation of Solid Catalyst

To a 1 L-volume glass reactor of which atmosphere was sufficientlysubstituted by nitrogen, equipped with a stirrer, 150 ml of toluene and20 g of spherical-shaped diethoxymagnesium having an average particlesize of 20 μm, particle distribution index of 0.86, bulk density of 0.35g/cc were added, while maintaining the temperature at 10° C. Then, 40 mlof titanium tetrachloride diluted in 60 ml toluene was added theretoover 1 hour, and then thereto a mixture of diethyl-2,3-diisopropylidenesuccinate 2.9 g and diethyl-2,3-diisopropylsuccinate 2.9 g was addedwhile increasing the reactor temperature to 110° C. After maintainingthe temperature at 110° C. for 2 hours and lowering to 90° C., stirringwas halted, the supernatant was removed, and the resultant was washedonce with additional 200 ml toluene. Thereto, 150 ml toluene and 50 mltitanium tetrachloride were added, and the temperature was raised up tonor and maintained for 2 hours for aging. After completion of the agingprocess, the mixed slurry was washed twice with 200 ml toluene for eachwashing, and then washed 5 times at 40° C. with 200 ml n-hexane for eachwashing, thereby obtaining a pale yellow solid catalyst component. Theobtained catalyst component was dried for 18 hours under a nitrogenstream, and the titanium content in the resulted solid catalystcomponent was 3.3 wt %.

2. Polypropylene Polymerization

Into a 4 L-volume high-pressure stainless reactor, 10 mg of thusobtained solid catalyst, 6.6 mmol of triethylaluminum and 0.66 mmol ofdicyclopentyldimethoxysilane were added. Next, 1000 ml of hydrogen and2.4 L of liquid propylene were added in this order and polymerizationwas carried out at an elevated temperature of 70° C. After 2 hours fromthe start of polymerization, the remaining propylene inside the reactorwas completely removed by opening the valve, while lowering the reactortemperature to room temperature.

Analysis of thus resulted polymer was carried out and the results wererepresented in Table 1.

The catalyst activity, stereoregularity, melt flow rate and molecularweight distribution were determined by the following method.

-   -   {circle around (1)} Catalyst activity (kg-PP/g-cat)=the amount        of polymers produced (kg)÷the amount of catalyst used (g)    -   {circle around (2)} Stereregularity (X.I.): the amount of        insolubles crystallized and precipitated in mixed xylene solvent        (wt %)    -   {circle around (3)} Melt flow rate (MFR): measured at 230° C.        under 2.16 kig load, according to ASTM 1238    -   {circle around (4)} Molecular weight distribution (P.I.):        determined by applying a modulation separation value obtained        from a parallel plate rheometer at 200° C. to the following        equation:

P.I.=54.6×(modulus separation value)^(−1.76)

Example 2

A catalyst was prepared according to the method described in Example 1except that a mixture of diethyl-2,3-diisopropylidenesuccinate 2.3 g anddiethyl-2,3-diisopropylsuccinate 3.5 g was used, instead of a mixture ofdiethyl-2,3-diisopropylidenesuccinate 2.9 g anddiethyl-2,3-diisopropylsuccinate 2.9 g in the above item 1. Preparationof solid catalyst. The titanium content of the resulted solid catalystcomponent was 3.2 wt %. Next, propylene polymerization was carried outby the same method as in Example 1, and the result was represented inTable 1.

Example 3

A catalyst was prepared according to the method described in Example 1except that a mixture of diethyl-2,3-diisopropylidenesuccinate 1.4 g anddiethyl-2,3-diisopropylsuccinate 4.3 g was used, instead of a mixture ofdiethyl-2,3-diisopropylidenesuccinate 2.9 g anddiethyl-2,3-diisopropylsuccinate 2.9 g in the above item 1. Preparationof solid catalyst. The titanium content of the resulted solid catalystcomponent was 3.1 wt %. Next, propylene polymerization was carried outby the same method as in Example 1, and the result was represented inTable 1.

Example 4

A catalyst was prepared according to the method described in Example 1except that a mixture of diethyl-2-isopropylidene-3-isopropylsuccinate2.9 g and diethyl-2,3-diisopropylsuccinate 2.9 g was used, instead of amixture of diethyl-2,3-diisopropylidenesuccinate 2.9 g anddiethyl-2,3-diisopropylsuccinate 2.9 g in the above item 1. Preparationof solid catalyst. The titanium content of the resulted solid catalystcomponent was 3.1 wt %. Next, propylene polymerization was carried outby the same method as in Example 1, and the result was represented inTable 1.

Comparative Example 1 1. Preparation of Solid Catalyst

To a 1 L-volume glass reactor of which atmosphere was sufficientlysubstituted by nitrogen, equipped with a stirrer, 150 ml of toluene, 12ml of tetrahydrofuran, 20 ml of butanol and 21 g of magnesium chloridewere added, and the temperature was raised to 110° C. and maintained for1 hour, thereby obtaining a homogenous solution. The resulted solutionwas cooled to 15° C., then added with 25 ml titanium tetrachloride, andthen, the reactor temperature was raised to 60° C. over 1 hour. Afteraging for 10 minutes, the mixture was stood still for 15 minute so as toprecipitate the carriers, and the supernatant was removed. To the slurryremained in the reactor, 200 ml toluene was added, and stirring,allowing to stand still and removal of the supernatant was carried outtwice for washing.

To the resulted slurry, 150 ml toluene was added, then 25 ml titaniumtetrachloride diluted in 50 ml toluene was further added at 15° C. over1 hour, and the reactor temperature was elevated to 30° C. at the speedof 0.5° C. per minute. The reaction mixture was maintained at 30° C. for1 hour, 7.5 ml of diisobutylphthalate was added, and then itstemperature was elevated to 110° C. at the speed of 0.5° C. per minute.

After maintaining the temperature at 110° C. for 1 hour and lowering to90° C., stirring was halted, the supernatant was removed, and theresultant was washed once with additional 200 ml toluene in the sameway. Thereto, 150 ml toluene and 50 ml titanium tetrachloride wereadded, and the temperature was raised to nor and maintained for 1 hoursfor aging. After completion of the aging process, the mixed slurry waswashed twice with 200 ml toluene for each washing, and then washed 5times at 40° C. with 200 ml n-hexane for each washing, thereby obtaininga pale yellow solid catalyst component. The obtained catalyst componentwas dried for 18 hours under a nitrogen stream, and the titanium contentin the resulted solid catalyst component was 3.3 wt %.

2. Polypropylene Polymerization

Polymerization was carried out according to the method described inExample 1 except using the above-obtained solid catalyst 10 mg, and theresult was represented in Table 1.

Comparative Example 2

A catalyst was prepared according to the method described in Example 1except that diethyl-2,3-diisopropylsuccinate 5.8 g was used, instead ofa mixture of diethyl-2,3-diisopropylidenesuccinate 2.9 g anddiethyl-2,3-diisopropylsuccinate 2.9 g in the above item 1. Preparationof solid catalyst. The titanium content of the resulted solid catalystcomponent was 2.8 wt %. Next, propylene polymerization was carried outby the same method as in Example 1, and the result was represented inTable 1.

Comparative Example 3

A catalyst was prepared according to the method described in Example 1except that diethyl-2-cyclohexylsuccinate 4.8 g was used, instead of amixture of diethyl-2,3-diisopropylidenesuccinate 2.9 g anddiethyl-2,3-diisopropylsuccinate 2.9 g in the above item 1. Preparationof solid catalyst. The titanium content of the resulted solid catalystcomponent was 3.8 wt %. Next, propylene polymerization was carried outby the same method as in Example 1, and the result was represented inTable 1.

TABLE 1 Melt Flow Molecular Activity Rate weight (kg-PP/g-Stereoregularity (MFR, distribution Cat) (X.I., wt. %) g/10 min) (P.I.)Example 1 42.0 98.0 2.2 7.0 Example 2 44.8 98.5 1.9 6.9 Example 3 45.998.6 1.7 6.8 Example 4 40.8 97.8 3.0 7.5 Com. 26.0 97.3 5.6 4.8 Example1 Com. 45.5 98.5 0.8 6.3 Example 2 Com. 22.7 97.8 2.5 5.0 Example 3

As seen from the above Table 1, Examples 1-4 according to the presentinvention show high catalyst activity and stereoregularity, excellentmelt flow rate and wide molecular weight distribution, whereasComparative example 1 and 3 show significantly low catalyst activity andnarrow molecular weight distribution; and Comparative example 2 showsnarrow molecular weight distribution and poor melt flow rate as comparedto the results of Examples 1-4 according to the present invention.

INDUSTRIAL APPLICABILITY

By using the solid catalyst prepared according to the method of thepresent invention, it is possible to prepare polypropylene having highmelt flowability, wide molecular weight distribution and excellentstereoregularity with a high production yield.

What is claimed is:
 1. A method for preparing a solid catalystcomprising the following steps: (1) reacting dialkoxymagnesium and atitanium halide, in the presence of an organic solvent; (2) adding aninternal electron donor selected from the compounds represented by thefollowing formula (II) together with another internal electron donorselected from the compounds represented by the following formula (IV) tothe resulted product from the above step (1), and mixing them together,while elevating the temperature to the range of 80-130° C.,

wherein, R¹, R², R³ and R⁴ are independently a linear, branched orcyclic C1-10 alkyl group or hydrogen;

wherein, R¹, R² and R⁴ are independently a linear, branched or cyclicC1-10 alkyl group or hydrogen; R³ is a linear, branched or cyclic C1-10alkyl group; and (3) reacting titanium halide with the resulted productfrom the above step (2) at the temperature range of 80-130° C. andwashing the resulted product.
 2. The method according to claim 1,wherein the solid catalyst comprises magnesium 5-40 wt %, titanium0.5-10 wt %, halogen 50-85 wt % and the internal electron donor mixture2.5-30 wt %.
 3. The method according to claim 1, wherein the internalelectron donor is selected from the following compounds:diethyl-2,3-dimethylsuccinate, diethyl-2,3-diethylsuccinate,diethyl-2,3-dipropylsuccinate, diethyl-2,3-diisopropylsuccinate,diethyl-2,3-dibutylsuccinate, diethyl-2,3-diisobutylsuccinate,diethyl-2,3-dipentylsuccinate, diethyl-2,3-dihexylsuccinate,diethyl-2,3-dicyclopentylsuccinate, diethyl-2,3-dicyclohexylsuccinate,diethyl-2-cyclopentyl-3-methylsuccinate,diethyl-2-cyclohexyl-3-methylsuccinate,diethyl-2-isopropyl-3-methylsuccinate,diethyl-2-isobutyl-3-methylsuccinate,diethyl-2-cyclopentyl-3-ethylsuccinate,diethyl-2-cyclohexyl-3-ethylsuccinate,diethyl-2-isopropyl-3-ethylsuccinate,diethyl-2-isobutyl-3-ethylsuccinate,diethyl-2-cyclopentyl-3-propylsuccinate,diethyl-2-cyclohexyl-3-propylsuccinate,diethyl-2-isopropyl-3-propylsuccinate,diethyl-2-isobutyl-3-propylsuccinate,diethyl-2-cyclopentyl-3-isopropylsuccinate,diethyl-2-cyclohexyl-3-isopropylsuccinate,diethyl-2-isobutyl-3-isopropylsuccinate,diethyl-2-cyclopentyl-3-isobutylsuccinate,diethyl-2-cyclohexyl-3-isobutylsuccinate,diethyl-2-isopropyl-3-isobutylidenesuccinate,diethyl-2-cyclopentyl-3-methylidenesuccinate,diethyl-2-cyclohexyl-3-methylidenesuccinate,diethyl-2-isopropyl-3-methylidenesuccinate,diethyl-2-isobutyl-3-methylidenesuccinate,diethyl-2-cyclopentyl-3-ethylidenesuccinate,diethyl-2-cyclohexyl-3-ethylidenesuccinate,diethyl-2-isopropyl-3-ethylidenesuccinate,diethyl-2-isobutyl-3-ethylidenesuccinate,diethyl-2-cyclopentyl-3-propylidenesuccinate,diethyl-2-cyclohexyl-3-propylidenesuccinate,diethyl-2-isopropyl-3-propylidenesuccinate,diethyl-2-isobutyl-3-propylidenesuccinate,diethyl-2-cyclopentyl-3-isopropylidenesuccinate,diethyl-2-cyclohexyl-3-isopropylidenesuccinate,diethyl-2-isobutyl-3-isopropylidenesuccinate,diethyl-2-cyclopentyl-3-isobutylidenesuccinate,diethyl-2-cyclohexyl-3-isobutylidenesuccinate,diethyl-2-isopropyl-3-isobutylidenesuccinate,diethyl-2-cyclopentylidene-3-methylsuccinate,diethyl-2-cyclohexylidene-3-methylsuccinate,diethyl-2-isopropylidene-3-methylsuccinate,diethyl-2-isobutylidene-3-methylsuccinate,diethyl-2-cyclopentylidene-3-ethylsuccinate,diethyl-2-cyclohexylidene-3-ethylsuccinate,diethyl-2-isopropylidene-3-ethylsuccinate,diethyl-2-isobutylidene-3-ethylsuccinate,diethyl-2-cyclopentylidene-3-propylsuccinate,diethyl-2-cyclohexylidene-3-propylsuccinate,diethyl-2-isopropylidene-3-propylsuccinate,diethyl-2-isobutylidene-3-propylsuccinate,diethyl-2-cyclopentylidene-3-isopropylsuccinate,diethyl-2-cyclohexylidene-3-isopropylsuccinate,diethyl-2-isobutylidene-3-isopropylsuccinate,diethyl-2-cyclopentylidene-3-isobutylsuccinate,diethyl-2-cyclohexylidene-3-isobutylsuccinate anddiethyl-2-isopropylidene-3-isobutylsuccinate.
 4. The method according toclaim 1, wherein the amount of the internal electron donor used is0.1-1.0 mole based on 1 mole of the dialkoxymagnesium.
 5. The methodaccording to claim 2, wherein the amount of the internal electron donorused is 0.1-1.0 mole based on 1 mole of the dialkoxymagnesium.
 6. Themethod according to claim 3, wherein the amount of the internal electrondonor used is 0.1-1.0 mole based on 1 mole of the dialkoxymagnesium.